title: A novel ferroceneylazobenzene self-assembled monolayer on an ITO electrode: photochemical and electrochemical behaviors.
abstract: A novel ferroceneylazobenzene self-assembled monolayer (SAM) has been constructed on an indium-tin oxide (ITO) electrode via the covalent attachment of 4-(4'-11-ferrocenyl-undecanoxyphenylazo)benzoic acid ( FcAzCOOH) onto a silanized ITO substrate surface and verified by reflectance infrared spectroscopy and water contact angle. Atomic force microscopy (AFM) and cyclic voltammogram (CV) indicated that the FcAzCOOH formed a uniform and reproducible SAM on the ITO electrode with a surface coverage of ca. 1.9 x 10 (-10) mol/cm (2) (87 A (2)/molecule). The reversible photoisomerization behavior of the SAM was characterized by UV-vis spectra. The azo pi-pi* transition band intensity of the SAM gradually decreased with UV (365 nm) irradiation and was almost recovered again when subsequent exposure to ambient room light (400-800 nm). The increased tilt angle of the molecules on the ITO substrate after UV irradiation further confirmed the trans-to- cis isomerization of azobenzene moieties. The CV of the trans- FcAzCOOH modified ITO electrode showed a pair of waves due to redox of the ferrocene groups in the potential range of 0 to +800 mV (vs SCE), and the peak separation of the redox wave became larger after UV irradiation and almost returned to its original value after subsequent exposure to the visible light. Rate-dependent CV curves indicated that the charge transfer rate between the ferrocene species in the SAM and the ITO electrode was slowed down after UV irradiation due to the smaller porosity of the monolayer film and the more compact barrier layer between the redox species and the ITO electrode. It is the first time to directly observe the influence of photoisomerization of the azobenzene moiety on the redox behavior of redox species in the ferroceneylazobenzene-functionalized SAM. The present results provide profound insight into the role of redox microenvironment on electron transfer kinetics and also provide a simple and facile approach to the preparation of photocontrollable electrodes.
authors.affiliation: Research Institute of Materials Science, South China University of Technology, Guangzhou, China.
authors.forename: Chongqing
authors.initials: C
authors.lastname: Li
authors.forename: Biye
authors.initials: B
authors.lastname: Ren
authors.forename: Yi
authors.initials: Y
authors.lastname: Zhang
authors.forename: Zhiyu
authors.initials: Z
authors.lastname: Cheng
authors.forename: Xinxing
authors.initials: X
authors.lastname: Liu
authors.forename: Zhen
authors.initials: Z
authors.lastname: Tong
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods*; D004566:Electrodes; D005296:Ferrous Compounds / Q000737:chemistry*; D007204:Indium / Q000737:chemistry; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D000075163:Metallocenes; D018625:Microscopy, Atomic Force / Q000379:methods; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010777:Photochemistry / Q000379:methods*; D013055:Spectrophotometry, Infrared / Q000379:methods; D017971:Tin Compounds / Q000737:chemistry*; D014466:Ultraviolet Rays
chemical_list: D001391:Azo Compounds; D005296:Ferrous Compounds; D000075163:Metallocenes; D017971:Tin Compounds; D007204:Indium; C109984:indium tin oxide; C009850:azobenzene; C045358:stannic oxide; C004998:ferrocene